JPH05230156A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition, using a curable phosphazene compound, having a high curing rate and capable of performing thick coating and providing a cured resin film excellent in surface hardness, transparency and weather resistance. CONSTITUTION:The objective curable resin composition is composed of (A) a curable phosphazene compound, (B) a polyfunctional acrylate-based compound such as dipentaerythritol hexaacrylate and (C) a crosslinking compound such as an acrylate- or a methacrylate-modified polymer, modified with epoxy and having <=6% curing shrinkage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more specifically, it uses a curable phosphazene compound and has a fast curing speed and can be applied thickly and has excellent surface hardness, transparency and weather resistance. The present invention relates to a curable resin composition capable of obtaining a cured resin film.

[0002]

A curable resin or a curable resin composition can be easily cured by irradiation with heat rays or active energy rays, and various coating materials, protective film forming materials, Widely used for filling and hardening materials. Among the curable resins, the curable phosphazene compound is particularly useful because it has excellent mechanical properties such as surface hardness and heat resistance. The curable phosphazene compound having such excellent properties has a problem that the curing speed is relatively slow. Therefore, for example, Japanese Patent Application Laid-Open No. 2-129210 discloses an improved technique. That is, a curable phosphazene compound is blended with a polyfunctional acrylate-based compound to increase the curing speed and enhance productivity. However, when the curable resin composition in which the polyfunctional acrylate compound or the like is mixed with the curable phosphazene compound is applied thickly, for example, when the film thickness exceeds 20 μm, the coating film is easily cracked or peeled off. have.

[0003]

Therefore, in view of the above situation, the present inventor has solved the problems of the conventional method and has a high curing speed, enables thick coating, and has a surface hardness, transparency, The inventors have conducted intensive studies to develop a curable resin composition that has excellent weather resistance and can obtain a cured resin surface that does not crack or peel. As a result, they have found that a curable resin composition having desired properties can be obtained by blending a compound having a low cure shrinkage ratio. The present invention has been completed based on such findings. That is, the present invention provides a curable resin composition comprising (A) a curable phosphazene compound, (B) a polyfunctional acrylate compound, and (C) a crosslinkable compound having a cure shrinkage of 6% or less. Is.

First, in the present invention, the curable phosphazene compound used as the component (A) is, for example, a compound represented by the general formula (I).

[0005]

[Chemical 1]

(In the formula, A represents a polymerization-curable group, B represents a non-polymerization-curable group, and a and b are 0 <a and 0 ≦ b.
And a real number that satisfies a + b = 2. ) And a phosphazene compound having a repeating unit represented by the formula (1), etc. In the formula,
A represents a polymerization-curable group, and the polymerization-curable group means a functional group that is cured by reaction with irradiation of ultraviolet rays, visible rays or electron beams, use of a chemical curing agent or heating,
Usually, it is a group having a reactive double bond. There are various groups having this reactive double bond. Examples thereof include functional groups containing an acryloyl group, a methacryloyl group, an allyl group or a vinyl group. The functional group containing an acryloyl group or a functional group containing a methacryloyl group, an acryloyloxy group or a methacryloyloxy group, further the general formula (II)

[0007]

[Chemical 2]

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 12 carbon atoms (preferably 1 to 5) (including a branched alkylene group). ] Is represented.

Specific examples of the group represented by the general formula (II) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxy-3-methylhexyl methacrylate, 5-hydroxyhexyl methacrylate, 3-hydroxy-2-t-butylpropyl methacrylate, 3-hydroxy-2,2-dimethylhexyl Removal of hydrogen atom from hydroxyl groups in methacrylates such as methacrylate, 3-hydroxy-2-methyl-2-ethylpropyl methacrylate and 12-hydroxydodecyl methacrylate. Residues, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxy -3-Methylhexyl acrylate, 5-hydroxyhexyl acrylate, 3-hydroxy-2-t-butylpropyl acrylate, 3-hydroxy-2,2-dimethylhexyl acrylate, 3-hydroxy-2-methyl-2-
Examples thereof include a residue obtained by removing a hydrogen atom from a hydroxyl group in acrylates such as ethylpropyl acrylate and 12-hydroxydodecyl acrylate. Particularly preferred groups are 2-hydroxyethyl methacrylate residue and 2-hydroxyethyl acrylate residue.
Further, the functional group containing an acryloyl group or a methacryloyl group can be a compound represented by the general formula (I
II)

[0010]

[Chemical 3]

(Wherein R ¹ and R ² are the same as above), that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of hydroxyalkyl-substituted (meth) acrylamide, and further represented by the general formula ( IV)

[0012]

[Chemical 4]

(In the formula, R ¹ is the same as the above.), That is, a residue obtained by removing one hydrogen atom from the amino group of acrylamide or methacrylamide may be mentioned. Furthermore, as the functional group containing an allyl group, in addition to the allyl group itself, for example, an allyloxy group (CH
₂ = CH-CH ₂ O-) it is not limited to this allyloxy group, broadly, the general formula (V) ~ (VII)

[0014]

[Chemical 5]

(Wherein R ¹ , R ³ and R ⁴ are the same as above), that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of an allyl compound having one hydroxyl group. You can Specific examples of the functional groups represented by the general formulas (V) to (VII) include:

[0016]

[Chemical 6]

There is a residue obtained by removing a hydrogen atom from a hydroxyl group in an allyl compound such as. On the other hand, B in the general formula (I) is
As described above, the general formulas (VIII), (IX)

[0018]

[Chemical 7]

(In the formula, M is an oxygen atom, a sulfur atom or
Represents a mino group, R^FiveIs an alkyl group having 1 to 18 carbon atoms
Or represents a halogenated alkyl group having 1 to 18 carbon atoms. Well
R ⁶~ R^TenAre independently hydrogen atom and halogen atom
Child, alkyl group having 1 to 4 carbon atoms or ha having 1 to 4 carbon atoms
A rogenated alkyl group is shown. ) Represents a group represented by. one
Specific examples of general formula (VIII) include methoxy group and ethoxy group.
Group, propoxy group, butoxy group, pentyloxy group,
Xyloxy group, heptyloxy group, octyloxy group
Group, decyloxy group, dodecyloxy group, hexadecyl
Oxy group, alkoxy group such as octadecyloxy group,
Substituted with halogen (eg fluorine, chlorine, bromine, etc.)
Similar alkoxy group, methylthio group, ethylthio group,
Propylthio group, butylthio group, pentylthio group, hex
Sylthio group, decylthio group, dodecylthio group, hexade
Acyl groups such as silthio, heptylthio, octylthio, etc.
Ruquilthio group, halogen (eg fluorine, chlorine, bromine
A similar alkylthio group, substituted with
Group, ethylimino group, propylimino group, butylimino
Group, pentylimino group, hexylimino group, heptylimine
Mino group, octylimino group, decylimino group, dodecyl
Imino group, hexadecylimino group, octadecylimino group
Alkylimino groups such as groups, halogens (eg fluorine,
Similar alkylimino groups substituted with chlorine, bromine, etc.)
Etc. can be mentioned. The group of formula (IX) is specifically
Is a phenoxy group, a thiophenyl group, a halogenated pheno group
Xy group (2,4,6-tribromophenoxy group, 4-butane)
Lomophenoxy group, 2-chlorophenoxy group, 2,4-
Dichlorophenoxy group) and halogenated thiophene
Nyl group (4-chlorophenylthio group etc.) or
Niline and aniline halides (2-chloroanili
1,2,4-dichloroaniline, 2,4,6-tribromine
Hydrogen atoms have been removed from the amino groups of moaniline etc.)
A residue etc. can be mentioned.

Regarding a and b in the above-mentioned general formula (I), 0 <a ≦ 2, 0 ≦ b <2, and a + b =
It may be any real number that satisfies 2, but preferably 0.6 ≦ a ≦
2,0 ≦ b ≦ 1.4. It should be noted that the substituent A is, when the phosphazene compound of the general formula (I) is polymerized (cured),
The substituent B is a group exhibiting a curing action, and the substituent B is a group exhibiting the action of adjusting the physical properties of the polymer and the polymerization performance. However, since those with a = 0 have no curability, such phosphazene compounds are excluded from the scope of the present invention. However, a = 2, b = 0,
That is,

[0021]

[Chemical 8]

The phosphazene compound having a repeating unit represented by the formula (A is the same as above) can be used as a raw material for the curable compound of the present invention, and the present invention is more effective in terms of curability. Can be specific. The curable phosphazene compound used in the present invention is preferably a curable phosphazene compound having a repeating unit of the above-mentioned general formula (I), but the degree of polymerization thereof is 3 or more, preferably 3 to 10,
The range is 000, more preferably 3 to 18, and most preferably 3 or 4 or a mixture thereof. Further, the repeating unit of the general formula (I) may be linked (polymerized) in a chain, but is preferably linked (polymerized) in a cyclic form. Specific examples of such a phosphazene compound are as follows.

[0023]

[Chemical 9]

On the other hand, the general formula (VI
In the group represented by II), when M is an oxygen atom, an alkanol represented by R ⁵ OH (wherein R ⁵ is the same as the above),
Using halogenated alkanol or its derivative, M
Is a sulfur atom, an alkylmercaptan represented by R ⁵ SH (wherein R ⁵ is the same as above), a halogenated alkylmercaptan or a derivative thereof is used, and when M is an imido group, R ⁵ NH ₂ R ⁵ is the same as the above), and an alkylamine, a halogenated alkylamine or a derivative thereof is used. In the group represented by the general formula (IX) introduced as the substituent B, when M is an oxygen atom, the general formula

[0025]

[Chemical 10]

(Wherein R ^{6 to} R ¹⁰ are the same as above), and when M is a sulfur atom, a general formula is used.

[0027]

[Chemical 11]

(Wherein R ^{6 to} R ¹⁰ are the same as above), and when M is an imide group, a general formula is used.

[0029]

[Chemical 12]

(In the formula, R ^{6 to} R ¹⁰ are the same as above.) An aniline or a derivative thereof is used. The compound forming the substituent A and the compound forming the substituent B are mixed with chlorophosphazene [a cyclic compound represented by the formula (NPCl ₂ ) _n or a compound represented by the formula Cl ₄ P. (NPCl ₂ ) _n-1.
The desired phosphazene compound of the general formula (I) can be obtained by reacting with a chain compound represented by NPCl ₃ (n is an integer of 3 or more, preferably 3 to 18) and the like. When the compound that forms is an alcohol, a mercaptan, a phenol or a thiophenol, an alkali metal such as metallic sodium or metallic potassium is reacted in advance to obtain an alcoholate, a phenolate, a mercaptide or a thiophenolate. In addition, it is preferable to use a dehydrohalogenating agent such as a tertiary amine in the reaction of the compound forming each of the above-mentioned substituents A and B with chlorophosphazene. Is, for example, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, Examples include -n-butylamine, pyridine, etc. Among them, pyridine is preferable, and this reaction is usually carried out in an organic solvent, such as benzene, toluene, xylene, chloroform, Examples thereof include cyclohexane, methylene chloride, tetrahydrofuran, 1,4-dioxane, etc. These can be used alone or in combination.The curable phosphazene compound obtained by the above reaction is chlorophosphazene as a raw material. It is preferable that all the chlorine atoms of the above are substituted with the above-mentioned substituents, but some chlorine may remain.By the reaction as described above, the curable phosphazene which is the main raw material of the phosphazene polymer is The compound is obtained.

Next, the polyfunctional (meth) acrylate compound used as the component (B) is a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate oligomer and a polyfunctional urethane (meth) acrylate. Is. Here, as the polyfunctional (meth) acrylate monomer, for example, 1,3-butanediol di (meth) acrylate; 1,4-butanediol di (meth) acrylate; 1,6-hexanediol di (meth) Acrylate; ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Difunctional compounds such as polyethylene glycol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, and trifunctional or higher polyfunctional compounds such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. Mention may be made of functional compounds.

As the polyfunctional (meth) acrylate oligomer, for example, polypentaerythritol poly (meth) acrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate, polyester (meth) acrylate, polyurethane (meth) acrylate, Epoxy (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, oligo (meth) acrylate, alkyd (meth)
Examples thereof include prepolymers having at least two (meth) acryloyl groups such as acrylate, polyol (meth) acrylate, and silicon (meth) acrylate. Among them, important prepolymers are polypentaerythritol poly (meth) acrylate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, polyester, epoxy, and polyurethane (meth) acrylate.

The polypentaerythritol poly (meth) acrylate is specifically represented by the general formula (X)

[0034]

[Chemical 13]

[In the formula, n is an integer of 1 to 4. And at least three of X are represented by the general formula (XI)

[0036]

[Chemical 14]

(In the formula, R ¹¹ represents hydrogen or a methyl group), and the rest represents an OH group. ] Is represented. The ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate is specifically represented by the general formula (XII)

[0038]

[Chemical 15]

(Wherein R ¹¹ is the same as above, m is 1, c
Is an integer of 1 to 6, d is 0 or an integer of 1 to 6, and c +
d = 6. ). Further, the polyester (meth) acrylate is, for example, ethylene glycol; 1,4-butanediol; 1,6-hexanediol; diethylene glycol, trimethylolpropane,
Polyhydric alcohols such as dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, and dipentaerythritol, and phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid alkenylsuccinic acid, etc. A polyester is obtained from a basic acid and then (meth) acrylated. Specific examples of such substances include adipic acid / 1,6-hesanediol / (meth) acrylic acid type, phthalic anhydride / propylene oxide / (meth) acrylic acid type, trimellitic acid / diethylene glycol / acrylic acid type Mention may be made of polyester (meth) acrylates such as

The above-mentioned epoxy (meth) acrylate is obtained by, for example, esterifying the epoxy group of an epoxy resin with (meth) acrylic acid to make the functional group a (meth) acryloyl group. Specific examples of such substances include, for example, bisphenol A-epichlorohydrin type epoxy resin / (meth) acrylic acid, phenol novolac-epichlorohydrin type epoxy resin / (meth) acrylic acid, alicyclic epoxy resin / (meth) acrylic acid. And epoxy (meth) acrylates such as The polyurethane (meth) acrylate can be obtained, for example, by reacting an isocyanate compound such as trilay diisocyanate with a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. it can. In this case, the central part of the molecule often has a polyester structure, and isocyanate groups are arranged at both ends to (meth) acrylate.

Further, the polyfunctional urethane (meth) acrylate is obtained by reacting a hydroxy group-containing (meth) acrylate with a polyisocyanate. Here, as the hydroxy group-containing (meth) acrylate, for example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane diacrylate, etc. A mixture, further the above compound and 2-hydroxyethyl acrylate,
A mixture of two or more kinds of 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate and the like can be mentioned. In such a mixture of two or more kinds, as a commercially available product, for example, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate of "A-TMM.3L" (manufactured by Shin-Nakamura Chemical Co., Ltd.),
There is a mixture of dipentaerythritol pentaacrylate and hexaacrylate of "DPHA" (manufactured by Nippon Kayaku Co., Ltd.). On the other hand, as the polyisocyanate, any of an aliphatic type, an aromatic type and an alicyclic type can be used,
For example, methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate;
2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, methylene bisphenyl diisocyanate and the like can be mentioned. Further, these may be a mixture of two or more kinds. Of these polyisocyanates, those which are non-yellowing polyurethanes are preferred.

The crosslinkable compound as the component (C) has a cure shrinkage of 6% or less, preferably 4.5% or less. There are various cross-linkable compounds having a curing shrinkage of 6% or less, and examples thereof include epoxy, urethane, alkyd urethane, polycaprolactone, unsaturated acid-modified drying oil, polyester and polyether. Examples include modified (meth) acrylate-modified polymers, curable (meth) acrylate monomers and halogenated polyesters. First, the (meth) acrylate-modified polymer contains UV-reactive acrylate groups in the polymer. Usually, these (meth) acrylate modified polymers have the general formula (XIII)

[0043]

[Chemical 16]

[In the formula, e is an integer of 1 to 5, and Polymer
r is an e-valent polymer, and Acrylate is a (meth) acrylic acid ester. ] Is represented. Here, the bifunctional polymer in which e is 2 has the following structure. Acrylate-Polymer-Acrylate Further, the trifunctional polymer in which e is 3 has the following structure.

[0045]

[Chemical 17]

Thus, a polymer having a monofunctional acrylate attached has the general formula (XIV)

[0047]

[Chemical 18]

(In the formula, Polymer and e have the same meanings as described above.) Further, the polymer to which the polyfunctional acrylate is bound has the general formula (XV)

[0049]

[Chemical 19]

(In the formula, Polymer and e are the same as above. Further, R ¹² is a divalent hydrocarbon group, and h is 1 to 1).
It is 6. ). And, a polymer in which both monofunctional and polyfunctional acrylate groups are bonded is represented by the general formula
(XVI)

[0051]

[Chemical 20]

(In the formula, Polymer, h and R ¹² are the same as above. Further, f and g are integers of 1 to 3, and f and g are
Does not exceed 5. ). Typical examples of such (meth) acrylate-modified polymers include those represented by the general formula (XVII)

[0053]

[Chemical 21]

(Wherein i is 1 to 20), an acrylate polyester represented by the general formula (XVIII)

[0055]

[Chemical formula 22]

(In the formula, i is 1 to 20) An acrylate epoxy represented by the general formula (XIX)

[0057]

[Chemical formula 23]

Examples include acrylate urethane represented by: Other (meth) acrylate modified polymers include (meth) acrylate alkyd urethane,
Examples thereof include (meth) acrylate polycaprolactone and (meth) acrylate unsaturated acid-modified drying oil.

Next, there are various curable (meth) acrylate monomers. Specifically, for example, (i) spiro acetal compound (b) (iso) cyanurate compound (c) melamine compound (d) compound having an aliphatic cyclic skeleton (e) compound having an aromatic cyclic skeleton Can be mentioned. First, as the (i) spiro acetal compound, for example, a compound represented by the general formula (XX)

[0060]

[Chemical formula 24]

[In the formula, R ¹¹ is the same as above, and R ¹³ is -C
(R ¹⁵ ) _3-j · R ¹⁶ (However, R ¹⁵ is hydrogen or has 4 carbon atoms.
The following alkyl group, R ¹⁶ represents a linear or branched alkylene group having 7 or less carbon atoms, an oxyalkylene group containing etheric oxygen, or a hydroxyalkylene group. ),
R ¹⁴ represents hydrogen or a methyl group, and j is an integer of 1 to 3. ] And / or general formula (XXI)

[0062]

[Chemical 25]

(In the formula, R ¹¹ and R ¹⁴ are the same as above.) A (meth) acrylate compound having a spiroacetal skeleton in the molecule.

The (b) (iso) cyanurate compound is an (iso) cyanurate compound having an (iso) cyanurate skeleton in the molecule, for example, the compound represented by the general formula (XXII)

[0065]

[Chemical formula 26]

[Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ represent a (poly) oxyalkylene group, Z ¹ , Z ² and Z ³ represent hydrogen, an alkyl group having 1 to 10 carbon atoms or a (meth) acryloyl group. Show. ] Or general formula (XXIII)

[0067]

[Chemical 27]

(In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , Z ¹ , Z ² and Z ³ are the same as described above.) And the like (meth) acryloyloxyalkyl (iso) cyanurate and the like. ..

(C) The melamine-based compound is a melamine compound having a melamine skeleton in the molecule, for example, a compound represented by the general formula (XXIV)

[0070]

[Chemical 28]

[Wherein R ²⁰ , R ²¹ and R ²² each independently represent hydrogen or a methyl group, R ²³ , R ²⁴ and R ²⁵ each independently represent an alkylene group having 2 to 10 carbon atoms, and R ²⁶ , R ²⁷ and R ²⁸ are hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or a general formula (XXV)

[0072]

[Chemical 29]

(In the formula, R ²⁹ is hydrogen or a methyl group,
R ³⁰ represents alkylene having 2 to 10 carbon atoms. ) Is a melamine group-containing (meth) acrylate compound.

Examples of the compound (d) having an aliphatic cyclic skeleton include compounds represented by the general formula (XXVI)

[0075]

[Chemical 30]

[In the formula, R ³¹ is COCHC═CH ₂ , or COC (CH ₃ ) C═CH ₂ . ] It is a (meth) acrylic acid ester compound containing the tricyclodecane group represented by these.

Examples of the compound (e) having an aromatic cyclic skeleton include those represented by the general formula (XXVII)

[0078]

[Chemical 31]

(In the formula, R ³² represents hydrogen or a methyl group,
k is 0 or an integer of 1 to 5, and Y is an alkylene group having 6 or less carbon atoms or one hydrogen atom of the alkylene group substituted with a hydroxyl group. These Ys are the same or different when k is 2 or more. ) Is a bifunctional compound.

Further, as the halogenated polyester, there is one obtained by halogenating a polyester polymer with a halogen element (fluorine, chlorine, bromine, etc.). This halogenated polyester is, for example, commercially available EBECRYL
584, 585, 586, 588 (manufactured by Daicel UCB Co., Ltd.) and the like can be used.

The present invention is a curable resin composition comprising the above components (A), (B) and (C).
In each of (A) and (B), (A) is 5 to 90% by weight, preferably 40 to 80% by weight, and (B) is 95 to 10% by weight.
It is blended in a weight ratio of 60 to 20% by weight. Then, the component (C) is blended in an amount of 5 to 70% by weight, preferably 10 to 50% by weight, based on the total amount of the above-mentioned blending ratios (A) and (B). Is used for various purposes. It should be noted that if the compounding ratio of the component (A) is less than 5% by weight, the mechanical strength will decrease, and if it exceeds 90% by weight, the curing rate will decrease, which is not preferable. And, the mixing ratio of the component (C) is 5
If it is less than 10% by weight, the weather resistance is deteriorated and the thick coating property remains unfavorable. On the other hand, if it exceeds 70% by weight, the surface hardness of the coating film decreases, which is not preferable.

The curable resin composition of the present invention comprises the above-mentioned components (A), (B) and (C). If necessary, various additives and other auxiliaries may be added to the present invention. It can be blended within a range that does not impair the purpose of. For example, the following can be used as the additive. That is, (a) stabilizers; quinone-based fillers such as hydroquinone; (b) fillers; inorganic substances (talc, calcium carbonate, ceramics powders, etc.), pigments, dyes, other organic substances (however, if transparency is lost, this is not possible. (C) Weather resistance additive; UV absorber, light stabilizer, antiaging agent, etc. (D) Other additives: antistatic agent, antifogging agent, lubricant, etc. (However, when transparency is lost In addition, as a curing accelerator, for example, when a curing method using ultraviolet light or visible light is used, as a photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoyl methyl ether, benzoin ethyl ether. , P-chlorobenzophenone,
It is preferable to add p-methoxybenzophenone, benzoyl peroxide, di-tert-butyl peroxide, camphorquinone and the like. These photopolymerization initiators may be used alone or in combination of two or more kinds.
The amount used is usually selected in the range of 0.05 to 10.0 parts by weight with respect to 100 parts by weight of the curable resin composition. When a heat curing method or a room temperature curing method is used, it is preferable to use a peroxide compound or an amine compound as a polymerization initiator, either alone or in combination.
Examples of the peroxide compound include benzoyl peroxide; p-chlorobenzoyl peroxide; 2,
4-dichlorobenzoyl peroxide; t-butyl hydroperoxide; di-tert-butyl peroxide; dicumyl peroxide; tert-butyl peroxyacetate; diacetate; tert butyl peroxybenzoate. And as an amine compound, for example, N, N-diethanol-p-
Toluidine; dimethyl-p-toluidine; p-toluidine; methylamine; tert-butylamine; methylethylamine; diphenylamine; 4,4'-dinitrodiphenylamine;o-nitroaniline;p-bromoaniline; 2,4,6-tribromo Aniline etc. can be mentioned. In this case, the total amount of the peroxide-based compound and the amine-based compound used is usually the curable resin composition 100.
It is usually selected in the range of 0.05 to 5.0 parts by weight with respect to parts by weight.

The curable resin composition of the present invention is usually used to provide a surface of a cured resin obtained by coating and curing it on a suitable substrate. The material of the base material is not particularly limited, and specifically, for example, polyester, polystyrene,
Acrylic resin, polycarbonate, polyurethane, polyethylene, polypropylene, polyamide resin, vinyl chloride resin, vinylidene chloride resin, polyalkylene terephthalate, polyarylate, polyarylene sulfide, etc., or a resin composition containing these resin components as a main component or these Examples thereof include a composite material containing a reinforcing material and the like. Of these, thermoplastic resins having relatively high heat resistance such as polyester, polycarbonate, and polyamide are preferable. The shape of the base material is not particularly limited, and may be, for example, a single-layer or multi-layer film shape or a sheet shape, or may be a shape after being formed into various molded products.

To apply the curable resin composition of the present invention onto the above-mentioned substrate, for example, spinner method, spray method,
A known coating method such as a roll coater method or a dipping method can be adopted. Then, in order to improve the workability when the curable resin composition of the present invention is applied onto the above-mentioned substrate, a diluent can be used. Specific examples of the diluent include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform and methylene chloride, methanol and ethanol. , Alcohols such as propanol and butanol, organic solvents such as ethers such as tetrahydrofuran and dioxane, and ethyl cellosolve and butyl cellosolve. These may be used alone or in admixture of two or more. Among these, ketones, alcohols and mixed solvents thereof are preferable, and particularly, mixed solvent containing methyl isobutyl ketone, isopropyl alcohol or butyl alcohol can be preferably used. When the diluent is used, the mixing ratio of the diluent and the curable resin composition of the present invention is not particularly limited, but is usually 1: 1 by weight ratio of diluent: curable resin composition.
It is selected in the range of 9 to 9: 1. In particular, mixing at a ratio of 9: 1 to 5: 5 is suitable in terms of workability.

To cure the curable resin composition of the present invention, for example, a room temperature curing method, a heat curing method or an active energy ray (electron beam, ultraviolet ray, X ray, γ ray or visible ray) is applied. There is a method of curing, and any method can be suitably used. Among these,
The method of irradiating with ultraviolet rays is particularly suitable. When using the method of irradiating ultraviolet rays, the wavelength is 200 to 550 nm.
UV light in the range of 0.1 seconds or more, preferably 0.5 to
Irradiation for 10 seconds is desirable. Further, the integrated light quantity of the irradiation light rays is usually 30 to 5,000 mJ / cm ² . The cured resin film obtained by curing the curable resin composition of the present invention is excellent in properties such as curing rate, expressed hardness, and transparency, and is also excellent in the balance of various properties, thus significantly improving the surface properties of the substrate. can do. In addition, this cured resin film is usually formed by applying the curable resin composition of the present invention without subjecting the surface of the substrate to surface treatment or undercoating with a primer, and by applying it once. Obtainable. However, depending on the type of the substrate, it is more preferable to perform surface treatment or primer treatment because the adhesiveness is further improved. Then, the thickness of the cured resin film obtained by applying the curable resin composition of the present invention,
It is preferably in the range of 0.01 to 1,000 μm. If this thickness is less than 0.01 μm, mechanical strength such as surface hardness may not be sufficient. In addition, 1,000 μm
When it exceeds, the flexibility of the base material itself may be deteriorated.

[0086]

EXAMPLES Next, the present invention will be described in more detail based on production examples and examples, but the present invention is not limited thereto. Production Example Production of Curable Phosphazene Compound In a 1 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, hexachlorocyclotriphosphazene [a cyclic compound of the formula (NPCl ₂ ) ₃ was added,
Hereinafter, it is abbreviated as 3PNC. ] 55.0 g (0.167 mol),
50 ml of toluene and 158 g of pyridine (2.
0 mol) was added and stirring was started. Next, 2-hydroxyethyl methacrylate (hereinafter, abbreviated as HEMA).
143 g (1.1 mol) was gradually added dropwise from the dropping funnel. In a warm bath, heat to 80 ° C and stir to react
Went on time. Next, the precipitated crystals and the solvent in the filtrate were removed by vacuum distillation, and the filtrate was thoroughly dried,
136 g of a yellow liquid 1,1,3,3,5,5-hexa (methacryloylethylenedioxy) cyclotriphosphazene (curable phosphazene compound) was obtained. Yield 91
%Met.

Examples and Comparative Examples Using the curable phosphazene compound obtained in the Production Example,
Each coating agent was prepared using the compounding ratio and the solvent shown in Table 1. The shrinkage rate of the coating agent thus prepared was measured. The shrinkage is the density C of the resin component of each coating agent before curing.
_A (Hubbert specific gravity measured by bottle method) and the density C _B of the cured product obtained by irradiating ultraviolet rays to the composition obtained by adding a proportion of benzophenone 5 wt% to the resin component (measured by the density method) Was calculated according to the following formula. Shrinkage = [1- (C _B / C _A)] × 100 Shrinkage measurement results are shown in Table 1. Note that the notes in the table are as follows. * 1: PPZ manufactured by Idemitsu Petrochemical Co., Ltd. * 2: Urethane acrylate VA-306H (pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer) manufactured by Kyoeisha Yushi Co., Ltd. * 3: Daicel UCB Co., Ltd. EBECRYL 584 * 4: SARTOMER Company SARTOMER 9505 * 5: Commercial product

[0088]

[Table 1]

Next, each coating agent was applied to a polycarbonate sheet having a thickness of 3 mm by a spray coating method, dried and then irradiated with ultraviolet rays of 250 mJ / cm ² to be cured to form a cured resin film having a thickness of 30 μm. Formed. The cured resin films obtained in the examples and comparative examples were checked for performance evaluation with respect to each item such as surface condition, surface hardness, pencil hardness, etc. of the cured resin film. The results of performance evaluation are shown in Table 2. The equipment and evaluation method used for evaluation of each item are as follows. Surface condition of the cured resin film Peeling, cracking, blistering, etc. were visually observed. Hardness A Taber abrasion tester was used. CS-10: 500 g, 100 times Pencil hardness 4H: No scratches can be obtained by rubbing with a pencil of 4H, but scratching can be obtained by rubbing with a pencil of 5H. 3H: Scratching with a 3H pencil does not hurt, but rubbing with a 4H pencil does. 2B: 2B pencil will not scratch, but rubbing with B pencil will scratch. Light transmittance Based on JIS K-7105. Cigarette resistance After cigarette (1) is spontaneously burned on the cured resin film,
The "yani" on the surface was wiped off with isopropyl alcohol, and the degree of "burn" of the cured resin film and the substrate was visually evaluated. Judgment Criteria: No change at all. Δ: A slight “burnt” mark is formed. X: Significant "burn" marks are formed. Weather resistance 4.1 of JIS D 0202 (General rules for coatings of automobile parts)
Conforms to item 6 (weather resistance test method). Test method A sunshine carbon arc lamp type weather resistance tester was used. Black panel temperature 63 ± 3 ℃, 60 minutes during irradiation 12
It is a spray cycle for 1 minute. The surface condition (swelling, peeling, cracks, stains, stains, etc.) of the cured resin film after 1,000 hours was visually evaluated.

[0090]

[Table 2]

[0091]

INDUSTRIAL APPLICABILITY As described above, the curable resin composition of the present invention can provide a cured resin film having excellent surface hardness, transparency, cigarette resistance and good scratch resistance. Therefore, the curable resin composition of the present invention can be effectively used for coating automobiles, building materials, wood products, flooring materials and the like.

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[Procedure amendment]

[Submission date] February 12, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

(In the formula, R ¹ is the same as above.
R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) A functional group represented by), that is, a residue obtained by removing a hydrogen atom from the hydroxyl group of an allyl compound having one hydroxyl group. Specific examples of the functional groups represented by the general formulas (V) to (VII) include:

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

On the other hand, the general formula (VI
In the group represented by II), when M is an oxygen atom, an alkanol represented by R ⁵ OH (wherein R ⁵ is the same as the above),
Using halogenated alkanol or its derivative, M
Is a sulfur atom, an alkylmercaptan represented by R ⁵ SH (wherein R ⁵ is the same as above), a halogenated alkylmercaptan or a derivative thereof is used, and when M is an imino group, R ⁵ NH ₂ (formula R ⁵ is the same as the above), and an alkylamine, a halogenated alkylamine or a derivative thereof is used. In the group represented by the general formula (IX) introduced as the substituent B, when M is an oxygen atom, the general formula

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

(Wherein R ^{6 to} R ¹⁰ are the same as above), and when M is an imino group, a general formula is used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

(Wherein R ¹¹ is the same as above, m is 1, c
Is an integer of 1 to 6, d is 0 or an integer of 1 to 6, and c +
d = 6. ). Further, the polyester (meth) acrylate is, for example, ethylene glycol; 1,4-butanediol; 1,6-hexanediol; diethylene glycol, trimethylolpropane,
Polyhydric alcohols such as dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, and dipentaerythritol, and polyhydric alcohols such as phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, and terephthalic acid alkenylsuccinic acid. A polyester is obtained from a basic acid and then (meth) acrylated. Specific examples of such substances include adipic acid / 1,6-hesanediol / (meth) acrylic acid type, phthalic anhydride / propylene oxide / (meth) acrylic acid type, trimellitic acid / diethylene glycol / acrylic acid type Mention may be made of polyester (meth) acrylates such as

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction content]

[0057]

[Chemical formula 23]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction content]

An acrylate urethane represented by the formula (wherein i is 1 to 20) and the like can be mentioned. Examples of other (meth) acrylate-modified polymers include (meth) acrylate alkyd urethane, (meth) acrylate polycaprolactone, and (meth) acrylate unsaturated acid-modified drying oil.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

Next, there are various curable (meth) acrylate monomers. Specific examples include (i) spiroacetal compounds (b) (iso) cyanurate compounds (c) melamine compounds (d) compounds having an aliphatic cyclic skeleton. First, as the (i) spiro acetal compound, for example, a compound represented by the general formula (XX)

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction content]

[0070]

[Chemical 28]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Delete

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0078

[Correction method] Delete

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Delete

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

The curable resin composition of the present invention comprises the above-mentioned components (A), (B) and (C). If necessary, various additives and other auxiliaries may be added to the present invention. It can be blended within a range that does not impair the purpose of For example, the following can be used as the additive. That is, (a) stabilizers; quinone-based fillers such as hydroquinone (b) fillers; inorganic substances (talc, calcium carbonate, ceramic powder, colloidal silica powder, etc.), pigments, dyes, other organic substances (however, transparency is (It is not possible to lose it.) (C) Weather resistance additive; UV absorber, light stabilizer, antiaging agent, etc. (D) Other additives; antistatic agent, antifogging agent, lubricant, etc. (However, transparency In addition, as a curing accelerator, for example, when a curing method using ultraviolet light or visible light is used, as a photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoylmethyl, etc. Ether, benzoin ethyl ether, p-chlorobenzophenone,
It is preferable to add p-methoxybenzophenone, benzoyl peroxide, di-tert-butyl peroxide, camphorquinone and the like. These photopolymerization initiators may be used alone or in combination of two or more kinds.
The amount used is usually selected in the range of 0.05 to 10.0 parts by weight with respect to 100 parts by weight of the curable resin composition. When a heat curing method or a room temperature curing method is used, it is preferable to use a peroxide compound or an amine compound as a polymerization initiator, either alone or in combination.
Examples of the peroxide compound include benzoyl peroxide; p-chlorobenzoyl peroxide; 2,
4-dichlorobenzoyl peroxide; t-butyl hydroperoxide; di-tert-butyl peroxide; dicumyl peroxide; tert-butyl peroxyacetate; diacetate; tert-butyl peroxybenzoate and the like. And as an amine compound, for example, N, N-diethanol-p
-Toluidine; dimethyl-p-toluidine; p-toluidine; methylamine; tert-butylamine; methylethylamine; diphenylamine; 4,4'-dinitrodiphenylamine;o-nitroaniline;p-bromoaniline; 2,4,6-tri Bromoaniline etc. can be mentioned. In this case, the total amount of the peroxide-based compound and the amine-based compound used is usually the curable resin composition 100.
It is usually selected in the range of 0.05 to 5.0 parts by weight based on parts by weight.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction content]

Next, each coating agent was applied to a polycarbonate sheet having a thickness of 3 mm by a spray coating method, dried and then irradiated with ultraviolet rays of 250 mJ / cm ² to be cured to form a cured resin film having a thickness of 30 μm. Formed. The cured resin films obtained in the examples and comparative examples were checked for performance evaluation with respect to each item such as surface condition, surface hardness, pencil hardness, etc. of the cured resin film. The results of performance evaluation are shown in Table 2. The equipment and evaluation method used for evaluation of each item are as follows. Surface condition of the cured resin film Peeling, cracking, blistering, etc. were visually observed. Surface hardness A Taber abrasion tester was used. CS-10: 500 g, 100 times Pencil hardness 4H: No scratches can be obtained by rubbing with a pencil of 4H, but scratching can be obtained by rubbing with a pencil of 5H. 3H: Scratching with a 3H pencil does not hurt, but rubbing with a 4H pencil does. 2B: 2B pencil will not scratch, but rubbing with B pencil will scratch. Light transmittance Based on JIS K-7105. Cigarette resistance After cigarette (1) is spontaneously burned on the cured resin film,
"Yani" on the surface was wiped off with isopropyl alcohol, and the degree of "burn" of the cured resin film and the substrate was visually evaluated. Judgment Criteria: No change at all. Δ: A slight “burnt” mark is formed. X: Significant "burn" marks are formed. Weather resistance 4.1 of JIS D 0202 (General rules for coatings of automobile parts)
Conforms to item 6 (weather resistance test method). Test method A sunshine carbon arc lamp type weather resistance tester was used. Black panel temperature 63 ± 3 ℃, 60 minutes during irradiation 12
It is a spray cycle for 1 minute. The surface condition (swelling, peeling, cracks, stains, stains, etc.) of the cured resin film after 1,000 hours was visually evaluated.

Claims (2)

[Claims] 1. A curable phosphazene compound (A),
A curable resin composition comprising (B) a polyfunctional acrylate compound and (C) a crosslinkable compound having a curing shrinkage of 6% or less. 2. The curable phosphazene compound (A) is 5 to
90% by weight and (B) a polyfunctional acrylate compound in an amount of 95 to 10% by weight, and (C) a crosslinkable compound having a curing shrinkage of 6% or less are (A) and (B).
The curable resin composition according to claim 1, which is 5 to 70% by weight based on the total amount of